US4029711A - 4-Hydroxy-n-butyraldehyde from allyl alcohol and formaldehyde - Google Patents
4-Hydroxy-n-butyraldehyde from allyl alcohol and formaldehyde Download PDFInfo
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- US4029711A US4029711A US05/672,362 US67236276A US4029711A US 4029711 A US4029711 A US 4029711A US 67236276 A US67236276 A US 67236276A US 4029711 A US4029711 A US 4029711A
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- United States
- Prior art keywords
- butyraldehyde
- formaldehyde
- hydroxy
- allyl alcohol
- hydrogen fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 66
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 title claims abstract description 21
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 description 20
- 235000019256 formaldehyde Nutrition 0.000 description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- OGOBEXBNRNHSEO-UHFFFAOYSA-N 4-prop-2-enoxybutanal Chemical compound C=CCOCCCC=O OGOBEXBNRNHSEO-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical class CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- JNODDICFTDYODH-UHFFFAOYSA-N 2-hydroxytetrahydrofuran Chemical compound OC1CCCO1 JNODDICFTDYODH-UHFFFAOYSA-N 0.000 description 1
- VVOBKXXECUQKBZ-UHFFFAOYSA-N 4-propoxybutan-1-ol Chemical compound CCCOCCCCO VVOBKXXECUQKBZ-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
Definitions
- the process of this invention relates to the production of 4-hydroxy-n-butyraldehyde by the hydrogen fluoride-catalyzed reaction of allyl alcohol and formaldehyde.
- 4-hydroxy-n-butyraldehyde is readily hydrogenated to prepare 1,4-butanediol, which is in turn reacted with terephthalic acid to produce a saturated polyester for fiber manufacture.
- 4-hydroxy-n-butyraldehyde may also be readily cyclized to form 2-hydroxy-tetrahydrofuran.
- the oxo synthesis comprises contacting an olefin with carbon monoxide and hydrogen in the presence of a cobalt salt at elevated temperatures and pressures.
- a typical example of the use of oxo chemistry to prepare 4-hydroxy-n-butyraldehyde is found in the article of Adkins and Krsek appearing at J. Am. Chem. Soc. 71, 3051-5 (1949).
- the oxo synthesis proceeds as follows:
- gamma-hydroxyaldehydes have also been synthesized from tetrahydrofuran by oxidation to prepare the peroxide which can be decomposed or rearranged to the aldehyde.
- British Pat. No. 614,392 (1948) is typical of this approach, and particularly suggests the use of cobalt or nickel catalysts to promote oxidation to the peroxide.
- 4-hydroxy-n-butyraldehyde can be prepared by contacting allyl alcohol with formaldehyde in the presence of hydrogen fluoride at a temperature within the range from about -100° C. to about 10° C.
- the present invention is based upon the finding that allyl alcohol and formaldehyde will react in the presence of hydrogen fluoride to produce 4-hydroxy-n-butyraldehyde.
- allyl alcohol is otherwise known as propenyl alcohol and has the structure ##STR1##
- Allyl alcohol is commercially available or may be prepared by hydrolysis of allyl chloride with dilute caustic.
- formaldehyde is a well-known organic chemical otherwise known as oxymethylene, formic aldehyde or methanal and has the structure ##STR2##
- Formaldehyde is commercially available or may be prepared by the catalytic oxidation of low-boiling petroleum gases such as methane or ethane.
- the reaction of allyl alcohol and formaldehyde is carried out in the liquid phase at a temperature within the range from about -100° C. to about 10° C., preferably about -70° C. to about -10° C., and at a pressure within the range from about 10 psia to about 1000 psia, preferably atmospheric.
- a catalyst comprising hydrogen fluoride is believed responsible for the relatively rapid and high conversions obtained under relatively mild reaction conditions.
- Hydrogen fluoride is also a solvent for the reaction, and is used in excess of catalytic amounts. Satisfactory conversions on the order of about 95% have been obtained in as little as 50 minutes using an HF:reactant weight ratio of from about 1:1 to about 10:1, preferably from about 2:1 to about 5:1.
- Hydrogen fluoride, per se is of course a suitable catalyst for use in the present process.
- non-interfering amounts of various diluents and contaminants may be present in the catalyst composition.
- suitable hydrogen fluoride catalysts comprise hydrogen fluoride, but may also comprise inert components such as water and dichloromethane.
- hydrogen fluoride is relatively easy to separate from the reaction zone effluent. Since the boiling point of HF is 19.7° C. at one atmosphere pressure, which is considerably more volatile than 4-hydroxy-n-butyraldehyde, the HF is readily separated by distillation and recycled to the reaction zone. Some unreacted formaldehyde may also be codistilled with HF and be recycled to the reaction zone.
- the molar ratio of formaldehyde to allyl alcohol which provides acceptable yields will vary depending upon precise reaction conditions. However, for general guidance, acceptable molar ratios of formaldehyde to allyl alcohol will range from about 1:1 to about 10:1, preferably from about 2:1 to about 4:1. Within these ranges it has been found that as the molar ratio of formaldehyde to allyl alcohol decreases below 2:1, increasing quantities of 4-allyloxy-n-butyraldehyde are found in the crude product.
- the crude reaction product comprising 4-hydroxy-n-butyraldehyde may be purified in any of several ways.
- hydrogen fluoride, and the unreacted formaldehyde and allyl alcohol may be removed by distillation under reduced pressure to leave 4-hydroxy-n-butyraldehyde as a bottoms product; or hydrogen fluoride and formaldehyde may be removed by distillation, and the butyraldehyde separated from allyl alcohol as a bisulfite addition compound, which is readily decomposed into the original aldehyde by contact with aqueous acid.
- the entire bottoms product after HF removal may be hydrogenated.
- the resulting diol may then be recovered by conventional distillation techniques.
- a 100-ml stainless-steel autoclave was charged with 8.7 grams (0.15 mols) of allyl alcohol, 9.0 grams (0.3 mols) of formaldehyde and 76 grams (3.8 mols) of hydrogen fluoride.
- the autoclave was maintained at about -45° C. for 50 minutes.
- Hydrogen fluoride was distilled from the reaction product and the distillation bottoms were analyzed by vapor phase chromatography using isobutyl alcohol as a standard.
- Example 2 shows that a strong protonic acid, such as sulfuric acid, completely inhibits the reaction, and thereby illustrates the uniqueness of hydrogen fluoride in this reaction.
- Example 3 produced more of the intermediate compound, 4-allyloxy-n-butyraldehyde, indicating a slower reaction at -70° C.
- Example 4 illustrates that catalytic hydrogenation gives a quantitative yield of 1,4-butanediol from the 4-hydroxy-n-butyraldehyde.
- Examples 5, 6, and 7 illustrate that water can be added to the reaction system.
- Example 7 also shows the rapid production of 4-allyloxy-n-butyraldehyde which is then converted to 4-hydroxy-n-butyraldehyde as the reaction proceeds.
- Example 8 indicates that a weak organic acid such as acetic acid may be present in the reaction medium.
- Example 9 shows that there is a rapid conversion of allyl alcohol, but that the yield of products is still low after only 20 minutes.
- Example 10 illustrates use of the preferred formaldehyde: allyl alcohol ratio of 2:1.
- Examples 11 and 12 show that an inert substance, such as dichloromethane may be present in the reaction medium.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for preparing 4-hydroxy-n-butyraldehyde which comprises contacting allyl alcohol with formaldehyde in the presence of hydrogen fluoride at a temperature in the range from about -100° C to about 10° C.
Description
The process of this invention relates to the production of 4-hydroxy-n-butyraldehyde by the hydrogen fluoride-catalyzed reaction of allyl alcohol and formaldehyde.
4-HYDROXY-N-BUTYRALDEHYDE HAS VARIOUS USES AS AN INTERMEDIATE IN THE PRODUCTION OF ORGANIC COMPOUNDS. For example, 4-hydroxy-n-butyraldehyde is readily hydrogenated to prepare 1,4-butanediol, which is in turn reacted with terephthalic acid to produce a saturated polyester for fiber manufacture. 4-hydroxy-n-butyraldehyde may also be readily cyclized to form 2-hydroxy-tetrahydrofuran.
It is known to produce butyraldehydes from unsaturated alcohols by the "oxo synthesis." The oxo synthesis comprises contacting an olefin with carbon monoxide and hydrogen in the presence of a cobalt salt at elevated temperatures and pressures. A typical example of the use of oxo chemistry to prepare 4-hydroxy-n-butyraldehyde is found in the article of Adkins and Krsek appearing at J. Am. Chem. Soc. 71, 3051-5 (1949). In general, the oxo synthesis proceeds as follows:
RCH.sub.2 CH═CH.sub.2 + CO+ H.sub.2 → R--CH.sub.2 CH.sub.2 CH.sub.2 CHO
gamma-hydroxyaldehydes have also been synthesized from tetrahydrofuran by oxidation to prepare the peroxide which can be decomposed or rearranged to the aldehyde. British Pat. No. 614,392 (1948) is typical of this approach, and particularly suggests the use of cobalt or nickel catalysts to promote oxidation to the peroxide.
It has now been discovered that 4-hydroxy-n-butyraldehyde can be prepared by contacting allyl alcohol with formaldehyde in the presence of hydrogen fluoride at a temperature within the range from about -100° C. to about 10° C.
The present invention is based upon the finding that allyl alcohol and formaldehyde will react in the presence of hydrogen fluoride to produce 4-hydroxy-n-butyraldehyde.
As is well recognized in the art, allyl alcohol is otherwise known as propenyl alcohol and has the structure ##STR1##
Allyl alcohol is commercially available or may be prepared by hydrolysis of allyl chloride with dilute caustic.
Similarly, formaldehyde is a well-known organic chemical otherwise known as oxymethylene, formic aldehyde or methanal and has the structure ##STR2##
Formaldehyde is commercially available or may be prepared by the catalytic oxidation of low-boiling petroleum gases such as methane or ethane.
In accordance with the process of the present invention, the reaction of allyl alcohol and formaldehyde is carried out in the liquid phase at a temperature within the range from about -100° C. to about 10° C., preferably about -70° C. to about -10° C., and at a pressure within the range from about 10 psia to about 1000 psia, preferably atmospheric.
Among other factors, the use of a catalyst comprising hydrogen fluoride is believed responsible for the relatively rapid and high conversions obtained under relatively mild reaction conditions. Hydrogen fluoride is also a solvent for the reaction, and is used in excess of catalytic amounts. Satisfactory conversions on the order of about 95% have been obtained in as little as 50 minutes using an HF:reactant weight ratio of from about 1:1 to about 10:1, preferably from about 2:1 to about 5:1. Hydrogen fluoride, per se, is of course a suitable catalyst for use in the present process. However, in actual practice, non-interfering amounts of various diluents and contaminants may be present in the catalyst composition. Thus, suitable hydrogen fluoride catalysts comprise hydrogen fluoride, but may also comprise inert components such as water and dichloromethane. In addition to superior activity as a catalyst in the present process, hydrogen fluoride is relatively easy to separate from the reaction zone effluent. Since the boiling point of HF is 19.7° C. at one atmosphere pressure, which is considerably more volatile than 4-hydroxy-n-butyraldehyde, the HF is readily separated by distillation and recycled to the reaction zone. Some unreacted formaldehyde may also be codistilled with HF and be recycled to the reaction zone.
The molar ratio of formaldehyde to allyl alcohol which provides acceptable yields will vary depending upon precise reaction conditions. However, for general guidance, acceptable molar ratios of formaldehyde to allyl alcohol will range from about 1:1 to about 10:1, preferably from about 2:1 to about 4:1. Within these ranges it has been found that as the molar ratio of formaldehyde to allyl alcohol decreases below 2:1, increasing quantities of 4-allyloxy-n-butyraldehyde are found in the crude product.
The crude reaction product comprising 4-hydroxy-n-butyraldehyde may be purified in any of several ways. For example, hydrogen fluoride, and the unreacted formaldehyde and allyl alcohol may be removed by distillation under reduced pressure to leave 4-hydroxy-n-butyraldehyde as a bottoms product; or hydrogen fluoride and formaldehyde may be removed by distillation, and the butyraldehyde separated from allyl alcohol as a bisulfite addition compound, which is readily decomposed into the original aldehyde by contact with aqueous acid. Also where the 4-hydroxy-n-butyraldehyde is intended as a feedstock in 1,4-butanediol production, the entire bottoms product after HF removal may be hydrogenated. The resulting diol may then be recovered by conventional distillation techniques.
The following examples illustrate the process of the invention. Those familiar with the art will recognize that modifications and variations of the illustrative examples may be made in the practice of the invention.
A 100-ml stainless-steel autoclave was charged with 8.7 grams (0.15 mols) of allyl alcohol, 9.0 grams (0.3 mols) of formaldehyde and 76 grams (3.8 mols) of hydrogen fluoride. The autoclave was maintained at about -45° C. for 50 minutes. Hydrogen fluoride was distilled from the reaction product and the distillation bottoms were analyzed by vapor phase chromatography using isobutyl alcohol as a standard.
Conversion of formaldehyde was essentially complete, i.e., over 95% and a 40.5% yield of 4-hydroxy-n-butyraldehyde was obtained.
In accordance with the general procedure of Example 1, 4-hydroxy-n-butyraldehyde was prepared under a variety of reaction conditions. The results are summarized in Table I.
TABLE I
__________________________________________________________________________
REACTION CONDITIONS PRODUCT
4-hydroxy-
4-allyloxy-
Allyl
Form- n-butyral-
n-butyral-
Ex.
Alcohol
aldehyde
HF H.sub.2 O
Other Temp.
Time
Conversion
dehyde
dehyde
No.
Mols Mols Mols
Mols
Name
Mols
° C.
Min.
% % % Other
__________________________________________________________________________
2 0.1 0.1 1.25
0 H.sub.2 SO.sub.4
0.26
-45 60 no reaction
3 0.13 0.13 2.5
0 none
-- -70 30 93 18 53 --
4 0.07 0.28 2.5
0 None
-- -45 30 90 -- -- --
60 >95 32.4
(1)
-- --
5 0.07 0.07 2.5
0.35
None
-- -30 30 high -- (2)
-- (2)
--
6 0.07 0.1 2.5
0.2
None
-- -45 30 95 -- -- --
60 >95 22 10 --
7 0.1 0.2 2.75
0.15
None
-- -45 60 -- -- (3)
-- (3)
--
90 -- 15 (3)
-- (3)
--
8 0.07 0.07 2.5
0 HOAC
0.21
-30 30 -- 6 14 --
9 0.07 0.17 2.5
0 None
-- -30 20 >95 -- (4)
-- --
10 0.07 0.17 2.5
0 None
-- -45 30 >95 34 18 1.2 (5)
11 0.1 0.2 2.5
0 CH.sub.2 Cl.sub.2
0.63
-45 60 >95 32 (6)
18 (6)
--
12 0.1 0.2 2.75
0.15
CH.sub.2 Cl.sub.2
0.63
-45 60 -- -- -- --
__________________________________________________________________________
Footnotes-
(1) Catalytic hydrogenation of the crude reaction product gave a 34% yiel
of 1,4-butanediol.
(2) Catalytic hydrogenation of the crude reaction product gave an 11%
yield of 1,4-butanediol and 16% yield of 4-propyloxybutanol.
(3) After 60 minutes the ratio of
4-hydroxy-n-butyraldehyde:4-allyloxy-n-butyraldehyde was 0.3; after 90
minutes the ratio was 3.0.
(4) Catalytic hydrogenation of the crude reaction product gave a 12% yiel
of 1,4-butanediol.
(5) 2,3-dihydrofuran.
(6) After 60 minutes the ratio of
4-hydroxy-n-butyraldehyde:4-allyloxy-n-butyraldehyde was 0.4; after 90
minutes the ratio was 2.7.
Example 2 shows that a strong protonic acid, such as sulfuric acid, completely inhibits the reaction, and thereby illustrates the uniqueness of hydrogen fluoride in this reaction. Example 3 produced more of the intermediate compound, 4-allyloxy-n-butyraldehyde, indicating a slower reaction at -70° C. Example 4 illustrates that catalytic hydrogenation gives a quantitative yield of 1,4-butanediol from the 4-hydroxy-n-butyraldehyde. Examples 5, 6, and 7 illustrate that water can be added to the reaction system. Example 7 also shows the rapid production of 4-allyloxy-n-butyraldehyde which is then converted to 4-hydroxy-n-butyraldehyde as the reaction proceeds. Example 8 indicates that a weak organic acid such as acetic acid may be present in the reaction medium. As in Example 7, Example 9 shows that there is a rapid conversion of allyl alcohol, but that the yield of products is still low after only 20 minutes. Example 10 illustrates use of the preferred formaldehyde: allyl alcohol ratio of 2:1. Examples 11 and 12 show that an inert substance, such as dichloromethane may be present in the reaction medium.
While the process of this invention has been illustrated by the above examples, various modifications will be apparent to those skilled in the art. Accordingly, the examples are not intended to limit the scope of the invention as defined by the following claims.
Claims (7)
1. A process for preparing 4-hydroxy-n-butyraldehyde which comprises contacting allyl alcohol and formaldehyde in the presence of hydrogen fluoride at a temperature from about -100° C to about 10° C and a pressure of from about 10 psia to about 1000 psia.
2. A process according to claim 1 wherein the hydrogen fluoride to reactant weight ratio is from about 1:1 to about 10:1.
3. A process according to claim 2 wherein the hydrogen fluoride to reactant weight ratio is about 5:1.
4. A process according to claim 1 wherein the molar ratio of formaldehyde to allyl alcohol is from about 1:1 to about 10:1.
5. A process according to claim 4 wherein the molar ratio of formaldehyde to allyl alcohol is from about 2:1 to about 4:1.
6. A process according to claim 1 wherein the temperature is from about -70° C to about -10° C and the pressure is atmospheric.
7. A process according to claim 1 wherein the molar ratio of formaldehyde to allyl alcohol is about 2:1, the hydrogen fluoride to reactant weight ratio is about 5:1, the temperature is from about -70° C to about -10° C, and the pressure is atmospheric.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/672,362 US4029711A (en) | 1976-03-31 | 1976-03-31 | 4-Hydroxy-n-butyraldehyde from allyl alcohol and formaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/672,362 US4029711A (en) | 1976-03-31 | 1976-03-31 | 4-Hydroxy-n-butyraldehyde from allyl alcohol and formaldehyde |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4029711A true US4029711A (en) | 1977-06-14 |
Family
ID=24698227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/672,362 Expired - Lifetime US4029711A (en) | 1976-03-31 | 1976-03-31 | 4-Hydroxy-n-butyraldehyde from allyl alcohol and formaldehyde |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US4029711A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2288211A (en) * | 1938-05-19 | 1942-06-30 | Chemical Marketing Company Inc | Process for the production of betaalkoxyaldehydes |
| US2967890A (en) * | 1961-01-10 | Process for preparing beta-aliphaticoxy- | ||
| US3519691A (en) * | 1964-07-24 | 1970-07-07 | Huels Chemische Werke Ag | O-hemiacetals of formaldehyde and catalytic process of manufacture |
-
1976
- 1976-03-31 US US05/672,362 patent/US4029711A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2967890A (en) * | 1961-01-10 | Process for preparing beta-aliphaticoxy- | ||
| US2288211A (en) * | 1938-05-19 | 1942-06-30 | Chemical Marketing Company Inc | Process for the production of betaalkoxyaldehydes |
| US3519691A (en) * | 1964-07-24 | 1970-07-07 | Huels Chemische Werke Ag | O-hemiacetals of formaldehyde and catalytic process of manufacture |
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